WO2013187787A1 - Procédé de conduite d'un processus de pyrolyse de déchets en plastique et/ou déchets en caoutchouc et/ou déchets organiques et utilisation d'un modificateur chimique dans ce procédé - Google Patents

Procédé de conduite d'un processus de pyrolyse de déchets en plastique et/ou déchets en caoutchouc et/ou déchets organiques et utilisation d'un modificateur chimique dans ce procédé Download PDF

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Publication number
WO2013187787A1
WO2013187787A1 PCT/PL2013/000078 PL2013000078W WO2013187787A1 WO 2013187787 A1 WO2013187787 A1 WO 2013187787A1 PL 2013000078 W PL2013000078 W PL 2013000078W WO 2013187787 A1 WO2013187787 A1 WO 2013187787A1
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Prior art keywords
weight
composition
waste
water
modifier
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Application number
PCT/PL2013/000078
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English (en)
Inventor
Marek Majcher
Wlodzimierz Przybylski
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DAGAS Sp. z.o.o.
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Publication date
Application filed by DAGAS Sp. z.o.o. filed Critical DAGAS Sp. z.o.o.
Publication of WO2013187787A1 publication Critical patent/WO2013187787A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/14—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot liquids, e.g. molten metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2207/00—Control
    • F23G2207/60—Additives supply
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2900/00—Special features of, or arrangements for incinerators
    • F23G2900/50202—Waste pyrolysis, gasification or cracking in presence of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

  • the object of the invention is the method of conducting a pyrolysis process of plastic waste, in particular polyolefinic, and/or rubber waste, particularly tires, and/or organic waste, such as biomass or municipal waste.
  • the solution is also related to the use of a chemical modifier in the pyrolysis process.
  • the developed solution relates to the field of plastics and other organic waste recycling carried out in a way which is minimally imposing on the environment, being particularly an alternative to waste incineration.
  • Thermal decomposition of plastics, rubber or organic substances may be carried out by pyrolysis, gasification, hydrocracking, and incineration, which is the least favorable for the environment.
  • the pyrolysis process is a long-known method of thermal degradation (destructive distillation) of polymeric substances. Pyrolysis can be a low-temperature process (200 - 450°C) or a high temperature process (550 - 850°C). Through heat treatment of the feed in the pyrolytic reactor, pyrolytic gas (dry gas), fuel fractions, oil fractions, and mazout are obtained. In the process, metal products (after processing e.g. of tires) and other solid products, such as carbon black and graphite, are obtained.
  • Patent PL 194973 Bl presents an installation to carry out the pyro lysis under atmospheric conditions or under elevated pressure or reduced pressure, which uses a tubular heating element, at the inlet of the heating pipe and in the interior thereof being located a burner.
  • the heating pipe needs to have a specific ratio between its diameter and length.
  • catalyst compositions are presented e.g. in the descriptions of the following applications: WO2007038903A1, RU2272826A1 or CN1786116A1.
  • the said catalysts have different functions - they reduce the temperature of the process, increase the efficiency of fuel fractions, accelerate the pyrolysis process or initiate it after bringing the pyrolytic mixture to a suitable temperature.
  • the object of the invention is a continuous process of pyrolysis of plastic waste and/or rubber waste and/or organic waste, comprising subjecting these components to a thermal decomposition in the pyrolytic reactor without any access to air, at a temperature of 200 to 850°C, under atmospheric pressure or elevated pressure or reduced pressure, characterized in that, into the pyrolytic reactor chamber, a composition of chemical modifier is dosed, which comprises 10 to 30% by weight of water, 20 to 80% by weight of at least one aliphatic alcohol, 5 to 15% by weight of carbamide or its derivatives of RiR 2 N(CO)NR 3 R 4 type, wherein Ri, R 2 , R 3 , R4 are the same or different and constitute C1-C6 alkyl groups, and 5 to 15% by weight of monoacetylfer
  • the composition before dilution, contains 10 to 30% by weight of water, 20 to 40% by weight of isopropanol, 20 to 40% by weight of n-butanol, 5 to 15% by weight of carbamide and 5 to 15% by weight of monoacetylferrocene, more preferably contains 1 to 25% by weight of water, 25 to 35% by weight of isopropanol, 25 to 35% by weight of n-butanol, 8 to 12% by weight of carbamide, and 8 to 12% by weight of monoacetylferrocene, preferably the modifier composition contains 20% by weight of water, 30% by weight of isopropanol, 30% by weight of n-butanol, 10% by weight of carbamide and 10% by weight of monoacetylferrocene.
  • 50 to 500 ml of the diluted modifier composition is dosed into the pyrolytic reactor per 1 ton of plastic waste and/or rubber waste and/or organic waste.
  • 50 to 150 ml of the diluted modifier composition is dosed per 1 ton of plastic waste, especially polyolefinic, or 300 to 500 ml of the diluted composition per 1 ton of rubber waste.
  • the method is carried out in a zero emission installation, devoid of direct outlet of gases generated in the process into the atmosphere.
  • the method is carried out in an airtight installation, under reduced pressure conditions, preferably under a pressure of 0.2 to 0.8 atm.
  • the object of the invention is also the use of a composition
  • a composition comprising 10 to 30%) by weight of water, 20 to 80% by weight of at least one aliphatic alcohol, 5 to 15% by weight of carbamide or its derivatives of RiR 2 N(CO)NR 3 R4 type, wherein R R 2 , R 3 , R4 are the same or different and constitute CrC 6 alkyl groups, and 5 to 15% by weight of monoacetylferrocene, to conduct the continuous pyrolysis of plastic waste and/or rubber waste and/or organic waste in the pyrolytic reactor without any access to air, at a temperature of 300 to 850°C, at atmospheric pressure or elevated pressure or reduced pressure, wherein the composition is diluted with water so that the diluted solution contains 5 to 15% by weight of the original composition.
  • the amount of carbon black generated in the process is globally reduced, and the deposition of quick coke on the elements of the pyrolytic reactor is reduced.
  • composition of the chemical modifier used in the method according to the invention was described in patent PL209480B1, where it was used under oxygen conditions in power boilers in combustion processes of solid, liquid and gas fuels.
  • the use of modifier assured "afterburning" of residual impurities in the boiler so that the resulting fuel gases had e.g. a lower content of CO.
  • Impurities containing carbon black were afterburned, with free access of air, to C0 2 .
  • additional energy gain from fuel combustion was achieved (complete combustion, afterburning of ashes).
  • the modifier in the pyrolysis process, has a positive effect - it acts selectively on the quick coke deposition processes, without any negative effects on the depolymerization processes occurring during pyrolysis (efficiency of the obtained fractions in not reduced).
  • the modifier composition used acts as a catalyst affecting selectively the transformations of the forming quick coke (carbon deposits).
  • the use of the above mentioned chemical modifier favors the formation of dry gas (mainly consisting of methane and ethane), in particular methane.
  • 12 to 18% by weight of the dry gases is obtained, and with the use of the modifier according to the invention, higher efficiencies may be obtained, in special conditions up to 70% by weight of the dry gases.
  • catalysts in addition to the above mentioned modifier, other known catalysts can be used.
  • Highly silicic additives, aluminosilicates (Si0 2 + ⁇ 1 2 0 3 ), catalysts based on zeolite, kaolin, oxides of rare earth metals, etc. are known as examples of catalysts used in the processes of pyrolysis.
  • an additional rutile - titanium catalyst (30% titanium/70% rutile) was used.
  • Catalysts of this type are primarily or only aimed at reducing the temperature of the pyrolysis process; therefore they can used in combination with the modifier composition based on ferrocene cyclopentadienyl complex, which in turn affects the chemical transformations that occur during the pyrolysis.
  • the main component of the modifier used in the method according to the invention is a complex which is a carrier of iron - monoacetylferrocene, or cyclopenta - 1,3 diene; 1 - (1 -cyclopenta - 2,4 - dienylideno) ethanolate of iron 2+ cation.
  • the presence of hydroxyl groups in the reaction medium is of decisive importance for the occuring transformations.
  • the modifier also contains a carbamide or its derivatives such as alkylurea of R 1 R 2 N(CO)NR3R 4 type, wherein Ri, R 2 , R 3 , 4 are the same or different and constitute Ci-C 6 alkyl groups, e.g. methylene or ethylene groups.
  • the aliphatic alcohols used in the modifier may have linear or branched chains.
  • Pyrolysis modifier should contain at least one alcohol (OH groups carrier).
  • the alcohol is selected from the C 2 - Cn group of alcohols, more preferably C3 - C 8 , especially C3-C6.
  • Ethanol, propanol, isopropanol, n-butanol, pentanol, heptanol and octanol are the examples of used alcohols.
  • the proportion of hydroxyl groups relative to the number of carbon atoms in the chain changes, and thereby the proportion of hydroxyl groups relative to the weight of the other components of the modifier changes.
  • the alcohols having intermediate chain lengths such as isopropanol and n-butanol. Therefore, preferably, the mixture of these two alcohols is used in the modifier.
  • the modifier may comprise only one alcohol from the said group or a mixture of three or four alcohols.
  • the modifier composition may also contain additives which do not affect its properties, e.g. colorants which allow to distinguish between different modifier compositions.
  • polyolefin plastics e.g. those based on polyethylene and polypropylene, but also other polymers based on heavier monomers (homopolymers and copolymers of PP, PS, and its copolymers, PVC, PA, and others) can be subjected to pyro lytic decomposition.
  • Rubber or caoutchouc waste which can be subjected to the process according to the invention is especially constituted by car tires.
  • Organic substances that can be subjected to pyrolysis are mainly constituted by biomass, that is, e.g. plant agricultural waste, wood, etc., or organic municipal waste varied in its composition.
  • the method according to the invention may also be used in waste forming mixtures of the above mentioned substances.
  • the amount of modifier in the method according to the invention depends on the processed raw material.
  • the heavier organic fractions are comprised in a given raw material, the more modifier is used per ton of raw material.
  • the method according to the invention can be carried out with additional catalysts and without them. It can be carried out under normal, elevated or reduced pressure.
  • Figure 1 an example of a preferred installation to carry out the pyrolysis using the method according to the invention was shown. It is an installation that provides zero-emission process, without access of air.
  • the zero emission process should be understood as devoid of any direct outlet of gases generated in the pyrolysis process into the atmosphere. All the resulting products are purified either by distillation in fractional column or by absorbers for the discharged gases. Purification of the discharged gases takes place also by contacting these gases with a water jacket in the vacuum pump with a rotating water ring.
  • the installation operates continuously in a closed system, so that all the sections are airtight, and are interconnected in a tight manner - to maintain the vacuum.
  • an engine acting as power generator is also included.
  • resulting pyrolytic gases are used as a fuel.
  • the installation meets high environmental standards regarding zero emission and trapping, in the adsorber and in the vacuum pump with water ring, undesirable impurities present in the resulting products.
  • the installation used for carrying out the method according to the invention is composed of a pyrolytic reactor 1 comprising reactor heating section 2 and a raw material feeder 3, wherein the feeder is provided with an airtight lock blocking the access of air to the reactor.
  • the reactor also includes a system 4 discharging solid residues from the reactor. Behind the reactor, there is a cyclone 5 (separator of solid particles, which then are discharged into the reactor), followed by a fractional column 6, which the waste material degradation products are brought to.
  • the installation is also provided with a heat exchangers 7, where the pyrolysis products are condensed, and with a final product tanks 8.
  • an engine 9 driven by pyrolytic gases charged directly from the installation was included.
  • the installation comprises a main heat exchanger 10 supplying an exchangers 7 and a fuel tank 1 1 supplying the reactor heating section, a compressor 12 and a separator 13, as well as a dephlegmator 15.
  • the installation is also provided with a pressure control system 14.
  • This system depending on the way the process is conducted, may provide the maintenance of a constant atmospheric pressure, or elevated or reduced pressure.
  • the system 14 includes a suction (vacuum) pump ensuring the maintenance, in the installation, of a reduced pressure of 0.1 to 0.9 atmospheres. Reduced pressure is achieved by sucking the pyrolytic gases from the entire installation.
  • the pyrolysis modifier is dosed into the reactor, preferably through a dispensing nozzle from an evaporator or an atomizer.
  • other dosages of the composition are also possible - e.g. gravity spraying or feeding the modifier together with the pyrolytic gases (or other gases) directed back to the reactor.
  • reactor does not contain any technical means for mixing the raw material subjected to pyrolysis.
  • the process takes place without mixing and, nevertheless, the beneficial effects of the carbon black (quick coke) not being deposited on parts of the reactor are observed. Thanks to the use of the pyrolysis modifier, it is possible to use structurally very simple pyrolytic reactors.
  • Composition B is a composition of Composition B:
  • Composition C is a composition having Composition C:
  • composition A The results of physicochemical properties analysis of the modifier (Composition A) are shown below.
  • Composition A was diluted with water as a carrier so that the following solutions were obtained:
  • PE + PP raw waste material in an amount of 20 tons was subjected to fragmentation, and, through an airtight lock of the feeder, it was introduced into the pyrolytic reactor.
  • Solution No 2 of the modifier (10% of composition A + 90% of water) was dosed into the reactor through a nozzle, which ensures the provision of the solution at a rate of 100 ml/hour.
  • the ratio of the dosed modifier solution was maintained at a level of about 100 ml of solution per 1 ton of the raw material subjected to pyrolysis.
  • 20 tons of raw material 2000 ml of solution was used. In a continuous process of pyrolysis, 20 tons of raw material was processed within 24 hours.
  • modifier solution When providing the reactor with another portion of the raw material, another proportional portion of the modifier solution was dosed (1000 ml of solution per 10 tons of raw material). Modifier solution was dosed at the initial stage in a continuous manner, and then, at intervals depending on other process parameters: temperature in the reactor, pressure, yield of fractions.
  • the use of the modifier in the pyrolysis processes of a mixture of plastics (PE + PP + 20% PA) - low-temperature process was carried out at 200-650°C under normal pressure.
  • PE + PP raw waste material in an amount of 20 tons was subjected to fragmentation, and, through an airtight lock of the feeder, it was introduced into the pyrolytic reactor.
  • Solution No 2 of the modifier (10% of composition A + 90% of water) was dosed into the reactor through a nozzle, which ensures the provision of the solution at a rate of 120 ml/hour.
  • the ratio of the dosed modifier solution was maintained at a level of 120 ml of solution per 1 ton of the raw material subjected to pyrolysis.
  • Pyrolysis process was carried out as in Example 4, but on a different kind of test installation to avoid damage to main installation by the retention of carbon black.
  • the modifier composition was not dosed into the reactor.
  • a comparative analysis of solid residues was performed.
  • the content of quick coke was about 85% higher in comparison with the process carried out with the participation of the modifier as in Example 4.
  • the quick coke retention was observed on its walls, where the strongest heating of the pyrolytic mixture occurred.
  • the process could not be carried out in a continuous manner. Some parts of the reactor, due to permanent contamination with coke, were replaced with new ones.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un processus continu de pyrolyse de déchets en plastique et/ou déchets en caoutchouc et/ou déchets organiques, comprenant la soumission de ces composants à une décomposition thermique dans le réacteur de pyrolyse sans aucun accès à l'air, à une température de 200 à 850 °C, sous pression atmosphérique ou pression élevée ou pression réduite, caractérisé en ce que, dans la chambre de réacteur pyrolytique, une composition de modificateur chimique est dosée, qui comprend de 10 à 30 % en poids d'eau, de 20 à 80 % en poids d'au moins un alcool aliphatique, de 5 à 15 % en poids de carbamide ou ses dérivés de type R1R2N(CO)NR3R4, où R1, R2, R3, R4 sont identiques ou différents et constituent des groupes alkyle en C1-C6, et de 5 à 15 % en poids de monoacétylferrocène, cette composition, avant distribution dans le réacteur, étant diluée en outre avec de l'eau, de sorte qu'après dilution, elle contienne environ 5 % en poids de composition et 95 % en poids d'eau à 15 % en poids de composition, et 85 % d'eau.
PCT/PL2013/000078 2012-06-12 2013-06-11 Procédé de conduite d'un processus de pyrolyse de déchets en plastique et/ou déchets en caoutchouc et/ou déchets organiques et utilisation d'un modificateur chimique dans ce procédé WO2013187787A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.399499 2012-06-12
PL399499A PL228284B1 (pl) 2012-06-12 2012-06-12 Sposób prowadzenia procesu pirolizy odpadowych tworzyw sztucznych i/lub odpadów gumowych i/lub odpadów organicznych oraz zastosowanie modyfikatora chemicznego w tym sposobie

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Publication Number Publication Date
WO2013187787A1 true WO2013187787A1 (fr) 2013-12-19

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EP (1) EP2674472A1 (fr)
PL (1) PL228284B1 (fr)
WO (1) WO2013187787A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111712535A (zh) * 2018-02-15 2020-09-25 株式会社普利司通 橡胶组合物制造方法
WO2021209276A1 (fr) 2020-04-17 2021-10-21 Nantek Hub S.L. Procédé de pyrolyse pour obtenir des produits pétrochimiques à partir de déchets plastiques
EP4155367A1 (fr) 2021-09-23 2023-03-29 Nantek Hub S.L. Processus de pyrolyse activé par des réactifs sans métal pour obtenir des carburants synthétiques à partir de déchets de plastique

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KR101455752B1 (ko) * 2013-04-22 2014-11-03 한국건설기술연구원 음식물 폐기물의 연료화 시스템 및 그 방법
EP3031881A1 (fr) 2014-12-08 2016-06-15 Innord sp. z o.o. S.K.A. Procédé de traitement pyrolytique de déchets de polymère depuis le recyclage d'emballages alimentaires et système permettant de mettre en oeuvre ce procédé
FR3045655B1 (fr) * 2015-12-16 2017-12-08 Michelin & Cie Procede de gazeification a lit fluidise de pneus

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WO2003104354A1 (fr) * 2002-06-05 2003-12-18 Izabella Bogacka Dispositif a pyrolyse a chauffage indirect pour les dechets en matiere plastique
PL194973B1 (pl) 2002-06-05 2007-07-31 Izabella Bogacka Urządzenie do pirolizy odpadowych tworzyw sztucznych
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WO2007038903A1 (fr) 2005-10-06 2007-04-12 Green Pluslink Company Limited Equipement industriel de pyrolyse continue de dechets et pneus usages
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PL209480B1 (pl) 2009-03-07 2011-09-30 Przedsiębiorstwo Wielobranżowe Prima Społka Z Ograniczoną Odpowiedzialno&Sac Modyfikator spalania paliw stałych, płynnych i gazowych, zwłaszcza drewna, gazu ziemnego, węgla, mazutu i innych węglowodorów, sposób modyfikowania procesu spalania paliw oraz zastosowanie modyfikatora spalania paliw
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111712535A (zh) * 2018-02-15 2020-09-25 株式会社普利司通 橡胶组合物制造方法
WO2021209276A1 (fr) 2020-04-17 2021-10-21 Nantek Hub S.L. Procédé de pyrolyse pour obtenir des produits pétrochimiques à partir de déchets plastiques
EP4155367A1 (fr) 2021-09-23 2023-03-29 Nantek Hub S.L. Processus de pyrolyse activé par des réactifs sans métal pour obtenir des carburants synthétiques à partir de déchets de plastique
WO2023046324A1 (fr) 2021-09-23 2023-03-30 Nantek Hub Sl Procédé de pyrolyse activé par des réactifs exempts de métal à base de nanocarbone pour obtenir des carburants synthétiques à partir de déchets plastiques

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